Copper-containing pyrazolone monoazo dyestuffs



United States Patent Int. Cl. (16911 45/18 US. Cl. 260-147 1 Claim ABSTRACT OF TI-Hl DISCLOSURE Copper-containing monoazo dyestuit of the formula wherein X represents a hydrogen or an alkali metal atom, and process for its preparation.

The present invention relates to a valuable coppercontaining monoazo dyestufi and to a process for its preparation; it relates especially to the dyestuff of the formula wherein X represents a hydrogen atom or an alkali metal atom, such as sodium or potassium. It has been found that the copper-containing monoazo dyestuif of the formula shown above can be prepared (a) By reacting with diethylamine in an aqueous medium, if desired under addition of alkaline agents, the copper complex dyestuii of the formula 3,461,111 Patented Aug. 12, 1969 "ice wherein Y represents a group of the formula CH CH -O- SO X or of the formula CH=CH and X has the above-mentioned meaning, or

(b) By preparing the dyestuft of the formula XOOC N 011 HO I SOa wherein X has the meaning given above, by diazotizing and coupling and by then treating it with copper-yielding agents.

When applying method (a) for the preparation of th new copper-containing monoazo dyestuff the process i: suitably carried out in such a way that, when using dyestufi containing a [i-hydroxyethyl-sulfonyl-sulfuric aci ester group, an aqueous solution which contains 1 molt of this starting compound in form of the alkali meta salt, is reacted with at least 2 moles of diethylamine a normal or elevated temperature and the dyestulf obtainer is then isolated by salting out, for example with sodium chloride or potassium chloride, and filtering or by spray drying of the reaction mixture.

The reaction described above may also be carried on with the same result by treating at room temperature 0 elevated temperature 1 mole of the starting dyestufl containing a ,B-hydroxyethylsulfonyl-sulfuric acid este group, in an aqueous solution with 1 to 1.2 mole o diethylamine in the presence of an alkaline agent sucl for example as sodium hydroxide or potassium hydroxide sodium carbonate or potassium carbonate or trisodiur phosphate.

Another way to prepare the new copper-containin monoazo dyestufi according to method (a) is to reac when using a copper complex dyestuff containing a viny' sulfonyl group, 1 mole of this starting compound i aqueous solution at room temperature or at elevated ten perature with 1 to 1.1 mole of diethylamine and the separating the dyestuff by spray-drying of the solutio1 The azo dyestuff free from metal which is necessai for the preparation of the new copper-containing monoaz dyestufi according to method (b) can be obtained t first converting the 6-(fi-hydroxy-ethylsulfonyl)-benzo: azolone, known from German patent specification NI 1,153,029, into the 6 (B-diethylamino ethylsulfonyl benzoxazolone and by then splitting it up by treating with sulfuric acid at to C. to form the l-amino-Z hydroxy 4 (fi-diethylamino-ethylsulfonyl)-benzene. Tl latter is diazotized according to usual methods and couple with 1-(4-sulfophenyl)-3-carboxy-pyrazolone-(5). Tl subsequent coppering of the coupling product thus 0' tained proceeds in known ways. Suitable copper-yieldir agents are water-soluble copper salts such, for exampl as sulfates, chlorides, acetates, formiates or the salts r organic sulfonic acids.

The separation by salting out of the copper-containii reaction product can be promoted by adding acids, sur as hydrochloric acid, sulfuric acid or acetic acid, to 1;] reaction mixture up to a pH value of S to 7.

The water-soluble copper complex dyestufi obtainr -S 02-0 Hr-O Ha- 2115):

according to the process of the present invention maybe used for dyeing cellulose materials, such as cotton, linen or viscose rayon. It is also appropriate for the dyeing of nitrogen-containing fibers of animal as well as of synthetic origin, such, for example as wool and polyamide fibers. The new dyestuff is moreover especially suitable for the printing of cellulose fibers. For this purpose it is printed in form of a thickening paste, which contains the dyestutf and an alkaline agent such, for example as sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate. The print is then subjected to a heat treatment, for example to a treatment with steam. The printing pastes used for the preparation of the prints which contain an alkaline agent are very resistant to the alkalies. In this respect the new dyestuff is essentially superior to the closest related dyestutf of the formula HOOC- --N= H known from the German patent specification No. 1,126,- 542.

The dyestutf obtained according to the process of the present invention has a high tinctorial strength. It may 9e used for producng yellow brown dyeings and prints )n cotton which prove a good fastness to washing, chlo- 'ine', water and rubbing and moreover a very good fastiess to light.

The following examples serve to illustrate the present nvention, but they are not intended to limit it thereto; he parts and percentages being by weight unless stated :therwise.

Example 1 130.7 parts of the dyestufi of the formula now-NU .-T=

1 form of the sodium salt were dissolved at about 30 to 3 C. in 1,000 parts by volume of water. The solution btained was mixed with 16 parts of diethylamine and )oled to about 24 to 27 C. by addition of 100 parts of e. At this temperature 24.2 parts of a sodium hydroxide )llltlOIl of 33% strength were given into the reaction ixture until a pH-value of 10.2 to 10.8 was obtained. he batch was then stirred for 16 hours at 18 to 22 C. id 20% of sodium chloride (referred to the volume of e solution) were added. In order to separate the product e pH-value of the dyestuff solution was adjusted to -5.2 by slowly introducing 48.0 parts of hydrochloric id of 30% strength. The precipitated dyestutf was filred ofi with suction, washed with a sodium chloride sotion of 15% strength and dried in vacuo at 70 to 80 C. '4.0 parts of a brown powder were obtained, which was sily soluble in water and which yielded on cotton, linen .regenerated cellulose in the presence of alkalies, such sodium carbonate, sodium hydroxide or trisodium osphate, yellow brown dyeings and prints of good ltllBSS to washing, chlorine, Water and rubbing and newer of very good fastness to light.

' Example2' Example 3 653.5 parts of the ester 'dyestulf of the formula given in Example 1 were dissolved at 65 to 70 C. in 5,000 parts by volume of water and 120 parts of anhydrous sodium carbonate were introducedat the same temperature. The reaction mixture showing an alkaline reaction (phenolphthalein) (pH-value=9.5 to 10) was stirred "for 30 minutes at 60 to 70 C. Then 3,000 parts of ground ice were added, thus lowering the temperature of the batch to about 30 C. parts of diethylamine-were then added to the batch and the whole was stirred for 20 to 25 hours at room temperature. By addition of l,600 parts of sodium chloride and 240 parts of hydrochloric acid of 30% strength the formed dyestuff precipitated at a pH- value of 5 to 5.2. The reaction product was filtered off with suction and washed with'a sodium chloride solution of 15% strength. After drying in vacuo at 60 to 70 C., 870 parts of .a brown powder were obtained, corresponding to the dyestulf prepared according to Example 1.

Example 4 555.5 parts of the dyestuff of the formula SO3H (prepared from the ester dyestulf of the formula given in Example 1 by treating it with alkali and by then precipitating it by salting out at a pH-value of 4.5 to 5.2) in form of the sodium salt were stirred in 3,000 parts by volume of water and mixed with 80 parts of diethylamine at room temperature. The dyestuff solution was stirred for another 20 hours and the product formed was isolated by spray-drying. 900 parts of a brown powder were obtained corresponding to the dyestufi prepared according to Example 1.

Example 5 243 parts of 6-(fi-hydroxy-ethylsulfonyl)-benzoxazolone were. added at 15 C. to 35 C. to 750 parts of sulfuric acid (of strength) and stirred overnight at room temperature. The thus obtained solution was given onto 6,500 parts of ice, mixed with parts of diethylamine and the pH-value was adjusted to 1212.5 at 5 C. to 10 C. by addition of 2,200 parts of a sodium hydroxide solution of 33% strength. At this pH-value the batch was stirred for about 5 hours at 5 to 10 C. and the pH- value of the reaction mixture was then adjusted to 6.5-7 by means of dilute hydrochloric acid. The suspension obtained was filtered off and washed with water. After drying in vacuo at 60 C., parts of fi-(fi-diethylaminoethylsulfonyl)-benzoxazolone which melts after recrystallization from alcohol at 161-l62 C'. were obtained.

An'alysis.C H O N S (molecular weight 298). Calculated: C, 52.4%; H, 6.0%; N, 9.4%. Found: C, 52.6%; H, 6.3%;N, 9.8%.

60 parts of the 6-( S-diethylamino-ethylsulfonyl)-benzoxazolone thus obtained were added at 60 to 70 C. to

130 parts of concentrated sulfuric acid and stirred for 90 minutes at 145 to 150 C. until the carbon dioxide evolution has ceased. After cooling 011, this solution was poured, while stirring, onto 400 parts of ice and then a portion of the sulfuric acid present in the mixture was neutralized at O to 5 C. by addition of 360 parts of a sodium hydroxide solution of 16.5% strength and of 400 parts of ice. The formed 1-amino-2-hydroxy-4-(fl-diethylamino-ethylsulfonyl)-benzene was then diazotized with 40 parts by volume of a 5 N sodium nitrite solution, the excess nitrite was destroyed by means of some amidosulfonic acid and the solution was neutralized with 88 parts of sodium bicarbonate.

56.8 parts of 1-(4'-sulfophenyl)-3-carboxy-pyrazolone- (5) were added to the solution of the diazo component thus obtained and the pH-value of the coupling mixture was adjusted to 6.7-7 by addition of 23 parts of sodium carbonate. When the coupling was terminated and 75 parts by volume of acetic acid of 50% strength have been added to the solution of the metal free dyestuif, 50 parts of copper sulfate containing crystal water and 50 parts of crystallized sodium acetate were added and the metallization mixture was heated for 1 to 2 hours up to 50-60 C. The coppering was then terminated. The copper complex dyestutf formed was salted out with sodium chloride, filtered oif with suction, washed with some sodium chloride solution of 15% strength and dried in vacuo at 50 to 60 C. 190 parts of a brown dyestutf powder were bin which X represents hydrogen, sodium or potassium.

References Cited UNITED STATES PATENTS 3,201,383 8/1965 Straley et a1. 260-147 FLOYD D. HIGEL, Primary Examiner DONALD M. PAPUGA, Assistant Examiner US. Cl. X.R. 

